Chromiferous azo-dyestuff and process of making same



Patented Mar. 5, 1935 UNITED STATES CHROMIFEROUS AZO-DYESTUFF ANDPROCESS OF MAKING SAME Fritz Straub, Basel, and Herman Schneider,Riehen, near Basel, Switzerland, assignors to Society of ChemicalIndustry in Basle, Basel,

Switzerland No Drawing. Application January 10, 1934, Se-

rial'No. 706,148. In Switzerland January 25,

1933 14 Claims.

The present invention relates to chromiferous azo-dyestufis. Itcomprises the process of making these dyestuifs as well as the newdyestuffs them selves.

It has been found that chromiferous azo-dvestufis are obtained bycausing azo-dyestufis of the general formula wherein R1 means asulfonated naphthalene radical and R2 a naphthol radical, and whereinthe hydroxyl group of the naphthalene radical R1 stands inortho-position to the azo-bridge, to react with agents yielding chromiumin such quantities that less than 1 atom of chromium devolves upon eachchromable group of the dyestufi molecule, the reaction being conductedin presence of soluble salts of organic acids.

Azo-dyestuffs of the above general formula may be obtained fromdifferent diazotized ortho-hydroxyaminonapththalene sulfonic acids bycoupling with different naphthols. Diazo compounds of suitableortho-hydroxyaminonaphthalene sulfonic acids are, for example, the diazocompounds of l-amino -2 -hydroxynaphthalene -4 -sulfonic acid,1-hydroxy-2-aminonaphthalene-e-sulfonic acid,l-amino-2-hydroxynaphthalene-6-sulionic acid,1-amino;2-hydroxynaphthalene-G-chloro-4- sulfonic acid,-l-amino-2-hydroxynapthalene-6- bromo4-sulfonic acid; further there mayalso be used as diazo components for example the nitratedl-diazo-2-hydroxynaphthalene-4 sulfonic acid and the nitratedl-diazo-Z-hydroxynaphthalene-G-sulfonic acid. Suitable couplingcomponents are aand fi-naphthol, as well as their substitution products,such as for example 8-chloro-a-naphthol and 5:8-dichloro-a-naphthol.

The treatment with the agents yielding chromium may take place in anopen vessel or under pressure, in the presence or absence of furtheradditions, such as, for example, inorganic salts, organic or inorganicacids, or in neutral or acid medium.

As agents yielding chromium there may be used chromium salts, such as,for example, chromium chloride, chromium fluoride, chromium sulfate,chromium sulfite, chromium acetate, chromium formats, chromium oxalate,the chromium salt of benzene-sulionic acid, or mixtures of such chromingagents.

As soluble salts of organic acids in whose presence the treatment withagents yielding chromium must be carried out in accordance with thepresent process, there come into consideration, for example, solublesalts of sulfonic acids and carboxylic acids of the aliphatic, aromaticand hydroaromatic series. Such salts are, for example, the alkali metalsalts, such as the sodium, potassium and ammonium salts of formic acid,acetic acid, propionic acid, oxalic acid, succinic acid, malonic acid,hexahydrobenzoic acid and hexahydrophthalic acid, or salts of the aminoacids, hydroxy acids, aminohydroxy acids, halogenated acids, nitratedacids, so-called exo-acids, such as w-benzylsulfonic acids, sulfamicacids, w-methanesulfonic acids, oxamic acids, amino-, monoandpolysulfonic acids of the benzene, naphthalene and anthracene series,the homologues, analogues and substitution products there of,naphthylamine-sulfonic acids, aminonaphtholsulfonic acids,arylcarboxylic acids such as benzoic acids, hydroxybenzoic acids,phthalic acids and the sulfonic acids thereof, such as sulfo-salicylicacids, sulfo-amino-salicylic acids or sulfo-phthalic acids; particularlyvaluable results, however, being obtained with the alkali metal salts ofaliphatic acids.

The chromiferous-azo-dyestufis obtainable according to the presentprocess dye animal fibers, such as, for example, wool and silk, blue toblack tints. They are considerably superior, with regard to the fastnessproperties, to the dyestuffs obtained from the same azo-dyestuffs bytreatment with the same quantities of the same chroming agent, but inthe absence of soluble salts of organic acids. Dyeing with the dyestuffsobtainable according to the present process can be carried out in theusual manner from a sulfuric acid bath or from dye baths which, besidesinorganic acids, contain aromatic acids, or advantageously according tothe process described in Patent No. 1,903,884.

The following examples illustrate the invention, the parts being byweight:--

Example 1 46,1 parts of the azo dyestufi from nitratedl-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene ofthe formula OH HO are stirred in 1000 parts of water. There are thenadded 4 parts of caustic soda solution of 30 per cent. strength, 12parts of sodium formate and a chromium fluoride solution correspondingwith 5,32 parts of CrzOs. The whole is thereupon boiled for 5 hours in areflux apparatus, and the black-violet solution thus obtained evaporatedto dryness on the water bath in a vacuum. The chromiferous dyestuffobtained dyes wool inv a bath containing organic acid and. sulfuric acidblack tints of excellent fastness.

Example 2 4,16 parts of the azo-dyestuff from diazotized2-amino-1-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene ofthe formula SOsH are dissolved in 100 parts of water containing 0.6 partof caustic soda solution of 30 per cent. strength. *A chromium formatesolution corresponding with 0,45 part of C1203, and 3 parts ofcrystallized sodium acetate are added to this solution and the wholeisboiled in a reflux apparatus for a long time. The blue solution thusobtained is filtered from small quantities of insoluble impurities, andafter concentrating the solution withaddition of common salt, thedyestuff is precipiated. The new chromium compound is obtained afterdrying in the form of a violet-black powder which is easily soluble inwater-to-a reddish-blue solution. In soda solution'of 10 per cent.strength, and in dilute caustic soda'solution, as well as inconcentrated sulfuric acid it dissolves to a greenish blue solution. Itdyes wool from a bath containing organic acid and sulfuric acid fastnavy blue tints.

Example 3 46,1 'parts of the azo-dyestufi from nitrated1--'-'diazo-2-hydroxynaphthalene-4-sulfonic acidand-2-hydroxynaphthalene of the formula SOsH Example 4 46,1 parts of theazo-dyestuff from nitrated 1diazo-2-hydroxynaphthalene-4-sulfonic acidand 2-hydroxynaphthalene are suspended in 1000 parts of Water. Afterstirring with 4 parts of caustic soda solution of 30 per cent. strengththere is added a chromium fluoride solution corresponding with 5,5 partsof Cl'zOs, as well as 36 parts of the sodium salt of benzene-sulfonicacid, and the whole is boiled in a reflux apparatus until unchromeddyestuff can no longer be detected. The filtered, violet-black solutionis evaporated to dryness in a vacuum. There is obtained a powder whichis easily soluble in water and dyes wool in a bath containing organicacid and sulfuric acid black tints of excellent fastness properties.

Example 5 46,1 parts of the azo-dyestuff from "nitrated1-diazo-2-hydroxynaphthalene-4-sulfonic acid and Z-hydroxynaphthaleneare suspended in 1200 parts of water. After stirring with 4 parts ofcaustic soda solution of 30 per cent. strength there is added a chromiumfluoride solution containing 5,4 parts of CrzO3, and 46 parts of thesodium salt of naphthalene-l-sulfonic acid, and the whole boiled for 6to 8 hours in a reflux apparatus. After filtering off small amounts ofimpurities the solution is evaporated to dryness in a vacuum. Thechromiferous dyestuff is obtained as a black powder which is easilysoluble in water and dyes wool in-a bath containing organic acid andsulfuric acid black tints of excellent fastness properties.

Example 6 46,1 parts of the azo-dvestuff from nitratedl-diazo-2-hydroxynaphthalene 4-sulfonic acid and 2-hydroxynaphthaleneare suspended in 1200 parts of Water which contains 4 parts by volume ofcaustic soda solution of 30 per cent. strength. .To this solution thereis added a chromium fluoride solution containing; 5,6; parts of C12O3,as well as 46 parts of the sod ium salt of naphthalene-2-sulfonic acidand the .whole boiled for 6 to 8 hours in-a reflux apparatus. Afterfiltering off small amounts of impurities the solution is evaporated todryness in a vacuum. The chromium compound which easily dissolves inwater to a brown-violetlplack; solution dyes wool in a bath containingorganic acid and sulfuric acid black tints of excellentfastness-properties.

Examp e 7 Into 1500 parts of water which contain 3 parts by volume ofcaustic soda' solution of 30 per cent; strength there areintroducedfwhile stirring, 46;1 parts-of the azo-dyestuff from nitrated-l -diazo- 2-hydroxynaphthalen'e-4- sulfonic jaci'd and2-hydroxynaphthalene. To "this solution there are added 50 parts ofthesodiun i'saltof l-aminonaphthalene-5-sulfonic acid and-chromiumfluoridesolution corresponding to 5,8 parts of 'C1'2O3. The whole is boiled for6 to 8 hours in a "reflux apparatus. The brown-violet black solutionthus obtained is then somewhat concentrated, filtered from mineral saltsthat have precipitate'd,=and evaporated to dryness. The new chromiumcompound dyes wool in a bath containing organicacid and sulfuric acidblack tints of very good fastness properties.

Example 8 41,6 parts of the azo-dyestuff from diazotizedl-amino-2-hydroxynaphthalene-4-sulfonic acid and l-hydroxynaphthalene ofthe formula SOBH for 6 to 8 hours in a reflux apparatus. After filteringoff small amounts of impurities and evaporating to dryness in a vacuumthe chromium compound formed is obtained in the form of a violet blackpowder. It dissolves freely in water, soda solution of 10 per cent.strength and caustic soda. solution of 10 per cent. strength to a bluesolution, and in concentrated sulfuric acid to a blue-green solution.The new chromiferous dyestuff dyes wool in a bath containing organicacid and sulfuric acid blue tints of good fastness properties.

Example 9 41,6 parts of the azo-dyestuff from diazotized1-amino-2-hydroxynaphthalene-4-sulfonic acid and l-hydroxynaphthaleneare dissolved in 900 parts of water containing 5 parts by volume ofcaustic soda solution of 30 per cent. strength. To this solution thereis added a chromium lactate solution containing 5,3 parts of CrzOx, aswell as 22 parts of the disodium salt of the 1-amino-4-sulfobenzene-2-carboxylic acid. The whole is boiled for about 6 hours ina reflux apparatus and after filtering off small amounts of impuritiesthe; chromium compound formed is isolated by evaporation to dryness in avacuum. It represents a violet-black powder and dissolves freely inwater, soda solution of 10 per cent. strength and caustic soda solutionof 10 per cent. strength to a blue solution. In concentrated sulfuricacid it dissolves to a blue-green solution and dyes wool in a bathcontaining organic acid and sulfuric acid blue tints of good fastnessproperties.

Example 10 49,5 parts of the azo-dyestufi from brominated1-diazo-2-hydroxynaphthalene-4-sulfonic acid and l-hydroxynaphthalene ofthe formula are dissolved in I00 parts of water containing 5 parts byvolume of caustic soda solution of 30 per cent. strength. To thissolution there is added a solution of the chromium salt of benzenesulfonic acid of about 3 per cent. strength containing 5,5 parts ofCrzOs, as well as 18 parts of sodium formate, and the whole is boiledfor 6 to 8 hours in a reflux apparatus. The solution is then evaporatedto dryness in a vacuum. The chromium compound. which is freely solublein water to a blue solution dyes wool in a bath containing organic acidand sulfuric acid blue tints of excellent fastness properties.

Example 11 49,5 parts of the azo-dyestuff from brominated1-diazo-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene ofthe formula OH HO SOsH are dissolved in 1000 parts of water containing 6parts by volume of caustic soda solution of 30 per cent. strength. Tothis solution there are added 40,8 parts of sodium acetate, aswell as achromium solution containing 4,5 parts of ClzOs, 2 parts of hydrofluoricacid, and 5 parts of formic acid of per cent. strength, and the whole isheated for 34 hours to C. After filtering off small amounts ofimpurities the blue solution obtained is concentrated and thechromiferous dyestuff precipitated by addition of common salt. Thechromium compound which is freely soluble in water dyes wool in a bathcontaining organic acid and sulfuric acid blue tints of excellent fastness properties.

Example 12 4,16 parts of the azo-dyestuff from 'diazotized 2amino-1-hyclroxynaphthalene-4-sulfonic acid and Z-hydroxynaphthalene ofthe formula 1 SOaH black powder which dissolves in water to areddishblue solution and dyes wool in a bath containing organic acid andsulfuric acid navy blue tints of good fastness properties.

Example 13 46,1 parts of the azo-dyestuff from nitratedldiazo-2-hydroxynaphthalene-4-sulfonic acid and l-hydroxynaphthalene ofthe formula are dissolved in 1000 parts of Water with addition of 5parts by volume of caustic solution of 30 per cent. strength. To thissolution there is added a solution of chromium formate containing 5,3parts of CI2O3, as well as 20 parts of sodium formate, and the whole isboiled for 6 to 8 hours in a reflux apparatus. The violet-black solutionof the chromium compound which has formed is evaporated to dryness in avacuum, if necessary after filtering off small amounts of impurities.There is obtained a black powder which dissolves in water to aviolet-black solution, and in soda solution of 10 per cent. strength andcaustic soda solution of 10 per cent. strength to a brown-violet blacksolution. The new dyestuff dissolves in con centrated sulfuric acid to agreen black solution. It dyes wool and silk in a bath containing organicacid and sulfuric acid black-tints of good fastness properties.

Example 14 41,6 parts of the azo-dyestufi from diazotizedlamino-2-hydroxynaphthalene-4-sulfonic acid and l-hydroxynaphthalene aredissolved in 7 parts by volume of caustic soda solution of 30 per cent.strength and 1000 parts of water. To this solution there is added achromium fluoride solution containing 5,4 parts of ClzOz, as well as 20parts of sodium formate, and the whole is boiled for 6 hours in a refluxapparatus. The blackish-blue solution which has formed is evaporated todryness in a vacuum, if necessary after filtering off small quantitiesof impurities. There is obtained a violet-black powder which freelydissolves in water, soda solution of per cent. strength and caustic sodasolution of 10 per cent. strength to a blue solution, and inconcentrated sulfuric acid to a blackish blue-green solution. The newchromiferous dyestuff dyes wool in a bath containing organic acid andsulfuric acid blue to navy blue tints of very good 'fastness properties.

Example 83,2 parts of the azo-dyestuff from diazotized lamino-2-hydroxynaphthalene--sulfonic acid and Z-hydroxynaphthalene of theformula OH HO are suspended in a pressure vessel in 1200 parts of water.To this suspension there are added 10 parts by volume of caustic sodasolution of per cent. strength, 30 parts of sodium formate, as well as achromium .formate solution corresponding with 8 parts of CIzOs, and thewhole is heated to 120 to 130 C. for 3 to 4 hours. After cooling, smallamounts of impurities are filtered off and the blackish blue solution isevaporated to dryness in a vacuum, a violet-black powder being obtained.The chromium compound which is freely soluble in water to a reddishblue, red dichroic solution dissolves also in soda solution of 10 percent. strength and in caustic soda solution of 10 per cent. strength toa reddish blue solution, whereas in concentrated sulfuric acid itdissolves to a greenish blue solution. The new dyestuff dyes W001 in abath containing organic acid and sulfuric acid fast navy blue tints.

What we claim is:-

1. Process for the manufacture of chromiferous azo-dyestuffs, consistingin causing azodyestuffs of the general formula R|N=N-R:

wherein R1 means a sulfonated naphthalene radical and R2 a naphtholradical, and wherein the hydroxyl group of the naphthalene radical R1stands in ortho-position to the azo-bridge, to re' act with agentsyielding chromium in such a proportion as to provide less than one atomof chromium to each chromable group of the dyestuff molecule. thereaction being conducted in presence of soluble salts of organic acids.

2. Process for the manufacture of chromiferous azo-dyestuffs, consistingin causing azodyestufis of the general formula wherein R1 meansv asulfonated naphthalene rad-. ical and R2 a naphthol radical, and whereinthe hydroxyl group of the naphthalene radical R1 standsin ortho-positionto the azo-bridge, to react with agents yielding chromium in such apro.- portion as to provide less than oneatom of chromium to eachchromable group of the dyestuif molecule, the reaction being conductedin presence of alkali metal salts of aliphatic acids. p

3. Process for the manufacture of chr'omif erous azo-dyestufis,nonsisting in causing the azodyestuff of the general formula a,-N=N

to react with agents yielding chromium in such a proportion as toprovide less than one atom of chromium to each chromable group of thedyestuff molecule. the reaction being conducted in presence of alkalimetal salts of aliphatic acids.

5. Process for the manufacture of chromiferous azo-dyestuffs, consistingin causing the amdyestuff of the formula SOaH to react with agentsyielding chromium in such a proportion as to provide less than one atomof chromium to each chromable group of the dyestuif molecule, thereaction being conducted in presence of alkali metal salts of aliphaticacids.

6. Process for the manufacture of a chromiferous azo-dyestuif,consisting in causing the amdyestufl of the formula $0311 to react withagents yielding chromium in such a ous azo-dyestuif, consisting incausing the azodyestuif of the formula OH HO- SO3H to react with agentsyielding chromium in such a proportion as to provide less than one atomof chromium to each chromable group of the dyestuff molecule, thereaction being conducted in presence of sodium formate.

8. Chromiferous azo-dyestuffs obtained by causing azo-dyestuffs of thegeneral formula wherein R1 means a sulfonated naphthalene radical and R2a naphthol radical, and wherein the hydroxyl group of the naphthaleneradical R1 stands in ortho-position to the azo-bridge, to react withagents yielding chromium in such a proportion as to provide less thanone atom of chromium to each chromable group of the dyestuff molecule,the reaction being conducted in presence of soluble salts of organicacids which products represent black powders dissolving in water to blueto black solutions and dyeing animal fibers fast blue to black tints.

9. Chromiferous azo-dyestuffs obtained by causing azo-dyestuifs of thegeneral formula I|t1N=N-Rz OH wherein R1 means a sulfonated naphthaleneradical and R2 a naphthol radical, and wherein the wherein R1 means asulfonated naphthalene radical and the hydroxyl group of the naphthaleneradical R1 stands in ortho-position to the azobridge, to react withagents yielding chromium in such a proportion as to provide less thanone atom of chromium to each chromable group of the dyestuff molecule,the reaction being conducted in presence of alkali metal salts ofaliphatic acids, which products represent black powders dissolving inwater to blue to black solutions and dyeing animal fibers fast blue toblack tints. 11.- Chromiferous azo-dyestuffs obtained by causing theazo-dyestulf of the general formula OH HO- to react with agents yieldingchromium in such a proportion as to provide less than one atom ofchromium to each chromable group of the dyestuif molecule, the reactionbeing conducted in presence of alkali metal salts of aliphatic acids,which products represent black powders dissolving in water to blacksolutions and dyeing wool fast black tints.

12. Chromiferous azo-dyestuffs obtained by causing the azo-dyestuif ofthe formula to react with agents yielding chromiumin such a proportionas to provide less than one atom of chromium to each chromable group ofthe dyestuif molecule, the reaction being conducted in presence ofalkali metal salts of aliphatic acids, which products represent blackpowders dissolving in water to blue solutions and dyeing wool fast blueto navy blue tints.

13. A chromiferous azo-dyestuif obtained by causing the azo-dyestufi ofthe formula to react with agents yielding chromium in such a proportionas to provide less than one atom of chromium to each chromable group ofthe dyestuff molecule, the reaction being conducted in presence ofsodium formate, which product represents a black powder dissolving inwater to a black solution and dyeing wool fast black tints.

14. A chromiferous azo-dyestulf obtained by causing the azo-dyestuff ofthe formula OH HO SOaH to react with agents yielding chromium in such aproportion as to provide less than one atom of chromium to eachchromable group of the dyestuff molecule, the reaction being conductedin presence of sodium formate, which product represents a black powder,dissolving inwater to a blue solution and dyeing wool fast blue to navyblue tints. i

FRITZ S'I'RAUB. HERMANN SCHNEIDER.

